CN110681354A - Preparation method of indium-based metal-organic framework - Google Patents
Preparation method of indium-based metal-organic framework Download PDFInfo
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- CN110681354A CN110681354A CN201910796883.4A CN201910796883A CN110681354A CN 110681354 A CN110681354 A CN 110681354A CN 201910796883 A CN201910796883 A CN 201910796883A CN 110681354 A CN110681354 A CN 110681354A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
Abstract
The invention relates to a preparation method of an indium-based metal-organic framework, which comprises the following steps: mixing indium nitrate, terephthalic acid and N, N-dimethylformamide, stirring for a certain time, adding sodium citrate as a regulator, continuously stirring, placing into a hydrothermal reaction kettle, heating at constant temperature for reaction, and naturally cooling to room temperature. After centrifugation, the porous MOFs material can be obtained by replacing in an absolute ethyl alcohol solution for 3 days. The material is simple to synthesize and convenient to operate, the size of the material is effectively changed, and the specific surface area of the raw material is greatly increased.
Description
Technical Field
The invention relates to a preparation method of an indium-based metal-organic framework.
Background
By the end of 20 years, with the rapid development of porous materials mainly comprising inorganic frameworks, in the cross field of inorganic material chemistry and coordination chemistry, a novel porous material: metal-organic Frameworks (MOFs) have been found to have characteristics of high specific surface area, large pore volume, large porosity, adjustability and the like, and are widely applied in a plurality of fields such as catalysis, gas storage, adsorption separation and the like, thereby becoming the focus of research in recent years.
The MILs series of MOFs were first assembled by F é rey, a professor of Versailles, France. Unlike other MOFs, the MIL-n series of materials is made of Al3+、Cr3+、Fe3+、In3+、Ga3+Different topological structures synthesized by trivalent cations and carboxylic acid ligands under solvothermal conditions are hot spots for domestic and foreign research due to high specific surface area and good stability.
Currently, MIL-68(In) is In3+Is an indium source, is dissolved in an organic solvent with an organic ligand for direct hydrothermal synthesis, and the BET specific surface area of the obtained product is about 654m2g-1When MIL-68(In) is used for adsorption, a smaller particle size, a larger specific surface area, and higher stability are required In order to increase the amount of adsorption applied.
Disclosure of Invention
The invention aims to provide a method for preparing an indium-based metal-organic framework with simple method and adjustable nucleation rate, and the indium-based metal-organic framework prepared by the method has the advantages of small size, uniform appearance and large specific surface area.
The invention adopts the following technical scheme:
a method for preparing an indium-based metal-organic framework, comprising the steps of:
(1) taking indium nitrate hydrate and terephthalic acid (H)2BDC) is dissolved in N, N-Dimethylformamide (DMF) to obtain a uniformly stirred mixed solution;
(2) uniformly stirring the mixed solution obtained in the step (1), adding a sodium citrate aqueous solution, and continuously and uniformly stirring;
(3) heating the mixed solution obtained In the step (2) at constant temperature, reacting for 0.5-48 h, and cooling to room temperature to obtain an In-MOFs primary product of the organic metal framework material;
(4) washing and centrifuging the primary In-MOFs product of the organic metal framework material, taking the lower-layer precipitate, and adding absolute ethyl alcohol to replace for 1 ~ 3 days;
(5) and (4) centrifuging the replaced precipitate In the step (4), and drying In vacuum overnight to finally obtain the adjusted indium-based metal-organic framework In-MOFs material.
In the step (1), the ratio of the amount of the substance of the hydrated indium nitrate to the amount of the substance of the terephthalic acid to the volume of the N, N-dimethylformamide is 1.05 ~ 1.35.35 mmol: 1.05 ~ 1.35.35 mmol: 15 ml.
In the step (2), the molar ratio of the sodium citrate aqueous solution to the indium nitrate hydrate is 0.1 ~ 0.34.34: 1.3.
In the step (2), the concentration of the sodium citrate aqueous solution is 0.5 ~ 1.7.7 mol/L.
In the step (3), the constant temperature heating temperature is 100 ~ 130 ℃.
In the step (3), the reaction time is 0.5 h.
In the step (4), N-dimethylformamide is used for washing the In-MOFs primary product of the organic metal framework material.
In the step (5), the temperature of vacuum drying is 60-100 ℃, and the drying time is 8-12 h.
The invention has the beneficial effects that: compared with the traditional method, the method adds sodium citrate for regulation, and can obtain a better indium-based metal-organic framework material sample through shorter synthesis time (30 min). The regulated material has the advantages of enhanced stability, increased reactive active sites, smaller particle size, uniform appearance, small and dense pore structure, capability of increasing the specific surface area of the material, and 1101.86m of the specific surface area2/g（BET）。
Drawings
FIG. 1 is an X-ray diffraction contrast (XRD) pattern of the materials obtained in example 1 and comparative example 1.
FIG. 2 is a Scanning Electron Micrograph (SEM) of the material obtained in example 1.
FIG. 3 is a Scanning Electron Micrograph (SEM) of the material obtained in comparative example 1.
FIG. 4 is a pore size diagram of the material obtained in example 1.
FIG. 5 is a pore size diagram of the material obtained in comparative example 1.
FIG. 6 is a BET bar graph comparing the BET bars of the materials obtained in example 1 ~, example 4, comparative example 1, and comparative example 2.
Detailed Description
The present invention will be described in detail with reference to the following examples and drawings. The scope of protection of the invention is not limited to the embodiments, and any modification made by those skilled in the art within the scope defined by the claims also falls within the scope of protection of the invention.
Example 1
1.3mmol of organic ligand H2BDC and 1.3mmol of hydrated indium nitrate are dissolved in 15ml of organic solvent N, N-dimethylformamide, and the mixed solution is put into a 70ml hydrothermal reaction kettle and stirred uniformly. Then 0.2ml of 0.2mol/L sodium citrate solution is added, the mixture is stirred evenly and reacts for 30min at the temperature of 100 ℃.
Washing with N, N-dimethylformamide for several times, centrifuging, placing the lower layer precipitate in a three-neck flask, adding appropriate amount of anhydrous ethanol, and replacing for three days. And after the replacement is stopped, collecting the product by centrifugal separation, heating to 60 ℃ at the speed of 5 ℃/min In a vacuum drying oven, and drying overnight to finally obtain the adjusted In-MOFs.
The pore volume of the adjusted In-MOFs prepared In this example was 0.40cm3(ii)/g; the aperture is 1.96 nm; BET of 1101.86m2/g。
Example 2
1.3mmol of organic ligand H2BDC and 1.3mmol of hydrated indium nitrate are dissolved in 15ml of organic solvent N, N-dimethylformamide, and the mixed solution is put into a 70ml hydrothermal reaction kettle and stirred uniformly. Then 0.2ml of 0.5mol/L sodium citrate solution is added, the mixture is stirred evenly and reacts for 30min at the temperature of 100 ℃.
Washing with N, N-dimethylformamide for several times, centrifuging, heating to 60 deg.C at 5 deg.C/min In a vacuum drying oven, and drying overnight to obtain the final In-MOFs.
The pore volume of the adjusted In-MOFs prepared In this example was 0.47cm3(ii)/g; the aperture is 2.10 nm; BET of 905.73m2/g。
Example 3
1.3mmol of organic ligand H2BDC and 1.3mmol of hydrated indium nitrate are dissolved in 15ml of organic solvent N, N-dimethylformamide, and the mixed solution is put into a 70ml hydrothermal reaction kettle and stirred uniformly. Then 0.2ml of 1.5mol/L sodium citrate solution is added, the mixture is stirred evenly and reacts for 30min at the temperature of 100 ℃.
Washing with N, N-dimethylformamide for several times, centrifuging, placing the lower layer precipitate in a three-neck flask, adding appropriate amount of anhydrous ethanol, and replacing for three days. And after the replacement is stopped, collecting the product by centrifugal separation, heating to 60 ℃ at the speed of 5 ℃/min In a vacuum drying oven, and drying overnight to finally obtain the adjusted In-MOFs.
The pore volume of the adjusted In-MOFs prepared In this example was 0.38cm3(ii)/g; the aperture is 1.91 nm; BET of 920.58m2/g。
Example 4
1.3mmol of organic ligand H2BDC and 1.3mmol of hydrated indium nitrate are dissolved in 15ml of organic solvent N, N-dimethylformamide, and the mixed solution is put into a 70ml hydrothermal reaction kettle and stirred uniformly. Then 0.2ml of 1.7mol/L sodium citrate solution is added, the mixture is stirred evenly and reacts for 30min at the temperature of 100 ℃.
Washing with N, N-dimethylformamide for several times, centrifuging, placing the lower layer precipitate in a three-neck flask, adding appropriate amount of anhydrous ethanol, and replacing for three days. And after the replacement is stopped, collecting the product by centrifugal separation, heating to 60 ℃ at the speed of 5 ℃/min In a vacuum drying oven, and drying overnight to finally obtain the adjusted In-MOFs.
The pore volume of the adjusted In-MOFs prepared In this example was 0.38cm3(ii)/g; the aperture is 1.99 nm; BET of 948.87m2/g。
Comparative example 1
1.3mmol of organic ligand H2BDC and 1.3mmol of hydrated indium nitrate are dissolved in 15ml of organic solvent N, N-dimethylformamide, and the mixed solution is put into 70ml of hydrothermal reactionThe mixture is stirred evenly in a kettle and reacts for 48 hours at 100 ℃.
Washing with N, N-dimethylformamide for several times, centrifuging, placing the lower layer precipitate in a three-neck flask, adding appropriate amount of anhydrous ethanol, and replacing for three days. After the displacement was stopped, the product was collected by centrifugation, warmed to 60 ℃ at 5 ℃/min In a vacuum oven and dried overnight to give MIL-68 (In).
Comparative example 2
1.3mmol of organic ligand H2BDC and 1.3mmol of hydrated indium nitrate are dissolved in 15ml of organic solvent N, N-dimethylformamide, and the mixed solution is put into a 70ml hydrothermal reaction kettle and stirred uniformly. Then 0.2ml of 1.0mol/L sodium citrate solution is added, the mixture is stirred evenly and reacts for 30min at the temperature of 100 ℃.
Washing with N, N-dimethylformamide for several times, centrifuging, placing the lower layer precipitate in a three-neck flask, adding appropriate amount of anhydrous ethanol, and replacing for three days. And after the replacement is stopped, collecting the product by centrifugal separation, heating to 60 ℃ at the speed of 5 ℃/min In a vacuum drying oven, and drying overnight to finally obtain the adjusted In-MOFs.
The pore volume of the adjusted In-MOFs prepared In this example was 0.31cm3(ii)/g; the aperture is 2.14 nm; BET of 585.97m2/g。
Effect example 1
X-ray diffraction (XRD) was performed on the In-MOFs obtained In example 1 and MIL-68(In) obtained In comparative example 1, and a comparison therebetween is shown In FIG. 1, In which (a) is MIL-68 (In); (b) are In-MOFs.
The XRD pattern shows that the diffraction peaks of the MIL-68(In) powder and the In-MOFs powder are matched to a higher degree, which indicates that the addition of the sodium citrate does not change the self structure of the MIL-68 (In).
Effect example 2
Scanning Electron Microscope (SEM) photographing was performed on the In-MOFs obtained In example 1 and the MIL-68(In) obtained In comparative example 1, as shown In FIGS. 2 and 3, wherein (a) is MIL-68 (In); (b) are In-MOFs.
As seen In the SEM image, the introduction of sodium citrate changes the appearance of MIL-68(In), and the appearance changes from a hexagonal rod shape to a rice grain shape with two tips of In-MOFs, and the grain size becomes smaller and the dispersion is more uniform.
Effect example 3
The pore size diagrams of the In-MOFs obtained In example 1 and the MIL-68(In) obtained In comparative example 1 are shown In FIGS. 4 and 5, respectively. Comparing the two figures, it can be seen that both materials are micro-meso mixed pores, and the number of In-MOFs micropores obtained In example 1 is significantly increased.
Effect example 4
For the histogram comparison of the specific surface areas of the In-MOFs obtained In example 4 of example 1 ~, the MIL-68(In) obtained In comparative example 1, and the In-MOFs obtained In comparative example 2, as shown In FIG. 6, the In-MOFs obtained In example 1 has the highest specific surface area, 1101.86m2/g。
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (8)
1. A preparation method of an indium-based metal-organic framework is characterized by comprising the following steps:
(1) dissolving indium nitrate hydrate and terephthalic acid in N, N-dimethylformamide to obtain a uniformly stirred mixed solution;
(2) uniformly stirring the mixed solution obtained in the step (1), adding a sodium citrate aqueous solution, and continuously and uniformly stirring;
(3) heating the mixed solution obtained In the step (2) at constant temperature, reacting for 0.5-48 h, and cooling to room temperature to obtain an In-MOFs primary product of the organic metal framework material;
(4) washing and centrifuging the primary In-MOFs product of the organic metal framework material, taking the lower-layer precipitate, and adding absolute ethyl alcohol for replacement;
(5) and (4) centrifuging the replaced precipitate In the step (4), and drying In vacuum overnight to finally obtain the adjusted indium-based metal-organic framework In-MOFs material.
2. The method for producing an indium-based metal-organic framework according to claim 1, wherein in the step (1), the ratio of the amount of the substance of indium nitrate hydrate, the amount of the substance of terephthalic acid and the volume of N, N-dimethylformamide is 1.05 ~ 1.35.35 mmol: 1.05 ~ 1.35.35 mmol: 15 ml.
3. The method of preparing an indium-based metal-organic framework as claimed in claim 1, wherein in step (2), the molar ratio of the aqueous solution of sodium citrate to the indium nitrate hydrate is 0.1 ~ 0.34.34: 1.3.
4. The method for producing an indium-based metal-organic framework as claimed in claim 1, wherein the concentration of the aqueous solution of sodium citrate in the step (2) is 0.2 ~ 1.7.7 mol/L.
5. The method for producing an indium-based metal-organic framework as claimed in claim 1, wherein the constant heating temperature in the step (3) is 100 ~ 130 ℃.
6. The method for producing an indium-based metal-organic framework as claimed in claim 1, wherein the reaction time in the step (3) is 0.5 h.
7. The method for producing an indium-based metal-organic framework as claimed In claim 1, wherein In the step (4), the organometallic framework material In-MOFs primary product is washed with N, N-dimethylformamide.
8. The method for preparing an indium-based metal-organic framework as claimed in claim 1, wherein the vacuum drying temperature in step (5) is 60 to 100 ℃ and the drying time is 8 to 12 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104415737A (en) * | 2013-08-23 | 2015-03-18 | 中国科学院大连化学物理研究所 | Magnesium-based metal organic framework material for methane-nitrogen adsorption separation and preparation |
| CN106512948A (en) * | 2016-10-21 | 2017-03-22 | 华南理工大学 | Metal-organic framework material MIL-68 (Al), and preparation method and application thereof |
| CN109821526A (en) * | 2019-02-20 | 2019-05-31 | 北京工业大学 | A kind of preparation method for constructing metal-doped indium oxide photocatalyst based on heteronuclear MOFs template |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104415737A (en) * | 2013-08-23 | 2015-03-18 | 中国科学院大连化学物理研究所 | Magnesium-based metal organic framework material for methane-nitrogen adsorption separation and preparation |
| CN106512948A (en) * | 2016-10-21 | 2017-03-22 | 华南理工大学 | Metal-organic framework material MIL-68 (Al), and preparation method and application thereof |
| CN109821526A (en) * | 2019-02-20 | 2019-05-31 | 北京工业大学 | A kind of preparation method for constructing metal-doped indium oxide photocatalyst based on heteronuclear MOFs template |
Non-Patent Citations (2)
| Title |
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| LI-NA JIN ET AL: "Size-controlled indium(iii)–benzenedicarboxylate hexagonal rods and their transformation to In2O3 hollow structures", 《CRYSTENGCOMM》 * |
| 张宏: "钴基MOF材料的合成及其性能测试与表征", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
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Application publication date: 20200114 |